Multicatalyst System in Asymmetric Catalysis

Preface xi

Contributors xiv

1 Toward Ideal Asymmetric Catalysis 1
Jian Zhou and Jin-Sheng Yu

1.1 Introduction 1

1.2 Challenges to Realize Ideal Asymmetric Catalysis 7

1.3 Solutions 13

1.4 Borrow Ideas from Nature 22

1.5 Conclusion 32

References 32

2 Multicatalyst System 37
Zhong-Yan Cao Feng Zhu and Jian Zhou

2.1 Introduction 37

2.2 Models of Substrate Activation 42

2.2.1 The Activation of Electrophiles 43

2.2.2 The Activation of Nucleophiles 54

2.2.3 SOMO Catalysis 64

2.3 Early Examples of the Application of Multicatalyst System in Asymmetric Catalysis 66

2.4 A General Introduction of Multicatalyst-Promoted Asymmetric Reactions 85

2.5 Classification of Multicatalyst-Promoted Asymmetric Reactions 95

2.6 Challenges and Possible Solutions 97

2.7 Multicatalyst System Versus Multifunctional Catalyst 103

2.8 Multicatalyst System Versus Additives-Enhanced Catalysis 105

2.9 Additive-Enhanced Catalysis 107

2.9.1 Nitrogen-containing Organobase 109

2.9.2 Inorganic Bases 111

2.9.3 H2O 114

2.9.4 Molecular Sieves and Dehydrators 120

2.9.5 N-oxide P-oxide and As-oxide 125

2.9.6 Alcohols and Phenols 129

2.9.7 Ammonium Halides and Metal Halides 133

2.9.8 Amides 137

2.9.9 Brønsted Acids and Lewis Acids 140

2.9.10 Two or More Additives Together 144

2.10 Conclusion 147

References 148

3 Asymmetric Multifunctional Catalysis 159
Jin-Sheng Yu and Jian Zhou

3.1 Introduction 159

3.2 Asymmetric Multifunctional Organocatalysis 164

3.2.1 H-Bond Donor-Tertiary Amine Catalysis 165

3.2.2 H-Bond Donor-Enamine Catalysis 193

3.2.3 H-Bond Donor-Phase Transfer Catalysis 203

3.2.4 H-Bond Donor-Tertiary Phosphine Catalysis 209

3.2.5 Chiral Phosphoric Acid Catalysis 214

3.2.6 Asymmetric Bifunctional Salt Catalysis 217

3.2.7 Miscellaneous 222

3.3 Asymmetric Hybrid Organo/Metal Catalysis 227

3.3.1 Brønsted Base/Lewis Acid Bifunctional Catalysis 228

3.3.2 Lewis Base/Lewis Acid Bifunctional Catalysis 233

3.3.3 Brønsted Acid/Lewis Acid Bifunctional Catalysis 236

3.3.4 Enamine/Lewis Acid Bifunctional Catalysis 238

3.3.5 Hemilable Trisoxazolines 240

3.4 Asymmetric Multifunctional Multimetallic Catalysis 242

3.4.1 Asymmetric Multifunctional Heteromultimetallic Catalysis 243

3.4.2 Asymmetric Multifunctional Homomultimetallic Catalysis 251

3.5 Anion-Enabled Bifunctional Asymmetric Catalysis 259

3.5.1 Ammonium Fluorides or Metal Fluorides 262

3.5.2 Metal Phosphates 265

3.5.3 Metal Carboxylates 265

3.5.4 Ammonium or Metal Aryloxides 269

3.5.5 Hydroxides and Alkoxides 271

3.5.6 Metal Amides 276

3.6 Conclusion 277

References 277

4 Asymmetric Cooperative Catalysis 291
Long Chen Yun-Lin Liu and Jian Zhou

4.1 Introduction 291

4.2 Catalytic Asymmetric Michael Addition Reaction 292

4.2.1 Combining Multiple Metal Catalysts 292

4.2.2 Combining Two Distinct Organocatalysts 293

4.2.3 Combining Metal Catalyst with Organocatalyst 297

4.3 Catalytic Asymmetric Mannich Reaction 299

4.3.1 Combining Lewis Acid Catalyst and Brønsted Base Catalyst 300

4.3.2 Combining Brønsted Acid Catalyst and Lewis Acid Catalyst 301

4.3.3 Combining Brønsted Acid Catalyst and Secondary Amine Catalyst 303

4.4 Catalytic Asymmetric Conia-Ene Reaction 304

4.4.1 Combining Chiral Lewis Acid and Achiral Lewis Acid 304

4.4.2 Combining Chiral Brønsted Base and Achiral Lewis Acid 306

4.5 Catalytic Asymmetric Umpolung Reaction 307

4.5.1 Combining NHC Catalyst and Lewis Acid Catalyst 307

4.5.2 Combining NHC Catalyst and Brønsted Acid Catalyst 313

4.6 Catalytic Asymmetric Cyanosilylation Reaction 315

4.7 a-Alkylation Reaction of Carbonyl Compounds 317

4.7.1 a-Alkylation of Carbonyl Compounds using Alcohols as Alkylation Reagents 317

4.7.2 a-Alkylation of Carbonyl Compounds through Benzylic C H Bond Oxidation 325

4.8 Catalytic Asymmetric Allylic Alkylation Reaction 326

4.8.1 Combining Achiral Transition Metal with Chiral LUMO-Lowering Catalysis 327

4.8.2 Combining Chiral Transition Metal Catalysis with Achiral Organocatalyst 331

4.9 Catalytic Asymmetric Aldol-Type Reaction 335

4.10 Catalytic Asymmetric (Aza)-Morita-Baylis-Hillman Reaction 338

4.10.1 Chiral Lewis Base/Achiral Acid Cocatalyzed (aza)-MBH Reaction 341

4.10.2 Achiral Lewis Base/Chiral Acid Cocatalyzed (aza)-MBH Reaction 342

4.11 Catalytic Asymmetric Hydrogenation Reaction 346

4.12 Catalytic Asymmetric Cycloaddition Reaction 350

4.12.1 [2 + 2] Reaction 351

4.12.2 [4 + 2] Reaction 352

4.13 Catalytic Asymmetric N H Insertion Reaction 356

4.14 Catalytic Asymmetric a-Functionalization of Aldehydes 358

4.15 Miscellaneous Reaction 360

4.16 Conclusion 364

References 365

5 Asymmetric Double Activation Catalysis by Multicatalyst System 373
Long Chen Zhong-Yan Cao and Jian Zhou

5.1 Introduction 373

5.2 Double Activation by Aminocatalysis and Lewis Base Catalysis 374

5.3 Asymmetric Double Primary Amine and Brønsted Acid Catalysis 378

5.3.1 Diels-Alder (DA)Reaction 379

5.3.2 Michael Addition 379

5.3.3 Epoxidation 386

5.3.4 Miscellaneous Reaction 390

5.4 Asymmetric Double Metal and Brønsted Base Catalysis 391

5.4.1 [3 + 2] Cycloaddition 392

5.4.2 Aldol Reaction 396

5.4.3 Miscellaneous Reactions 399

5.5 Asymmetric H-Bond Donor Catalysis and Lewis Base Catalysis 401

5.6 Sequential Double Activation Catalysis 404

5.7 Conclusion 408

References 408

6 Asymmetric Assisted Catalysis by Multicatalyst System 411
Xing-Ping Zeng and Jian Zhou

6.1 Introduction 411

6.2 Asymmetric Assisted Catalysis within Acids and Bases 414

6.2.1 Acid Assisted Acid Catalysis 415

6.2.2 Base Assisted Brønsted Acid Catalysis 433

6.2.3 Lewis Base Assisted Brønsted Base Catalysis 435

6.2.4 Acid Assisted Base Catalysis 437

6.2.5 Miscellaneous 439

6.3 Modulation of a Metal Complex by a Chiral Ligand 443

6.3.1 Modulation of a Chiral Metal Complex with a Chiral Ligand 444

6.3.2 Asymmetric Deactivation Activation and Deactivation/Activation 451

6.3.3 Asymmetric Activation of Racemic Catalysts Bearing Tropos Ligand 460

6.4 Supramolecular-Type Assisted Catalysis 462

6.5 Conclusion 469

References 469

7 Asymmetric Catalysis Facilitated by Photochemical or Electrochemical Methods 475
Zhong-Yan Cao and Jian Zhou

7.1 Introduction 475

7.2 Catalytic Asymmetric Reaction Facilitated by Photochemical Method 476

7.2.1 Asymmetric Oxidation Reactions 477

7.2.2 a-Functionalization of Tertiary Amines 479

7.2.3 a-Functionalization of Aldehydes 482

7.2.4 [2 + 2] Photocycloaddition Reaction 488

7.2.5 Miscellaneous Reactions 489

7.3 Catalytic Asymmetric Reactions Facilitated by Electrochemical Method 493

7.4 Conclusion 497

References 498

8 Multicatalyst System Realized Asymmetric Tandem Reactions 501
Feng Zhou Yun-Lin Liu and Jian Zhou

8.1 Introduction 501

8.1.1 Basic Models of MSRATR 502

8.1.2 Challenges and Solutions for the Development of MSRATR 507

8.2 Multicatalyst Systems of Homocombination 509

8.2.1 By Multiple Metal Catalysts 509

8.2.2 By Multiple Organocatalysts 522

8.2.3 By Multiple Enzymes 558

8.3 Hetero Combination System Realized MSRATR 566

8.3.1 By Combination of Metal and Organocatalysts 566

8.3.2 By Combination of Metal Catalysis and Biocatalysis 604

8.3.3 By Combination of Organocatalysis and Biocatalysis 620

8.4 Conclusion 622

References 623

9 Waste-Mediated Reactions 633
Jian Zhou and Xing-Ping Zeng

9.1 Introduction 633

9.2 Historical Background 636

9.3 Waste-Promoted Single Reactions 637

9.3.1 Waste Act as a Brønsted Base 638

9.3.2 By-product as Lewis Base 649

9.4 By-Products as Acidic Promoter 653

9.5 Waste-Promoted Tandem Reactions 654

9.6 Waste-Catalyzed Tandem Reactions 657

9.7 Conclusions 666

References 667

10 Multicatalyst System Mediated Asymmetric Reactions in Total Synthesis 671
Yun-Lin Liu and Jian Zhou

10.1 Introduction 671

10.2 Application of Multicatalyst System Mediated Single Reactions 672

10.3 Application of Multicatalyst Mediated Tandem Reaction 677

10.4 Conclusion 685

References 686

Index 689